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Helical polymers, ubiquitous in biological systems, exhibit dual dynamic behaviour â transitioning between disordered and helical conformations, and depolymerizing to monomers â that arises from the presence of both noncovalent and covalent bonds in their architectures. Now, a team led by Qi Zhang, Da-Hui Qu and Ben Feringa has developed a fully synthetic helical polymer that folds and recycles by combining disulfides and amino acids in a single system. The cover image shows an artistic representation of a dual dynamic helical polymer that unfolds to depolymerize into small molecules.
The partial hydrogenation of multi-substituted allenes is a highly useful reaction but impeded by difficult selectivity control. Now, pincer cobalt catalysts enable this transformation through metalâligand cooperative interactions, achieving ligand-controlled selective allene semihydrogenation in a divergent manner.
Per- and polyfluoroalkyl substances are widely utilized across various fields such as energy and electronics industries, but concerns have been raised about their environmental accumulation. Now, recent studies have revealed methods to decompose these compounds into reusable fluorine sources, enabling a circular economy.
Chemical upcycling of waste plastic is challenging because of its heterogeneous nature. Now, a newly designed single-site organo-nickel catalyst cuts through the mix by selectively snipping branched CâC linkages, allowing for the separation of polyolefin mixtures.
High-entropy materials offer an exciting realm of possibilities for material discovery and application; however, their nanoscale synthesis is limited by the need for specialized equipment. Now, a simple synthetic strategy employing wax candles enables production of these compositionally complex nanomaterials.
The programmability of synthetic cells facilitates their application as drug delivery devices, but on-demand biosynthesis and release of cargo using a tissue-penetrating stimuli remains a challenge. Now, the heat generated from magnetic hyperthermia â a clinically approved anticancer therapy â is used to control the in situ synthesis and release of biomolecules from within synthetic cells.
Real-time single-molecule observation provides insights into transient intermediates that are normally inaccessible using ensemble measurements. This Review discusses the use of nanopores as both single-molecule nanoreactors and single-molecule sensors for elucidating reaction pathways and kinetics, while highlighting their potential to control covalent reactions under confinement.
Covalent polymers with helical conformations offer an adaptive scaffold for smart materials, but polymer-to-monomer deconstruction is inhibited by the covalent backbone. Now it has been shown that poly(disulfide)s can be folded into helices driven by side-chain hydrogen-bonding self-assembly, resulting in a synthetic helical polymer that can be fully recycled.
The hydrogenation of multisubstituted allenes presents a long-standing challenge due to the difficulty in simultaneously controlling multiple selectivity parameters. Now a class of pincer cobalt catalysts featuring multiple metalâligand cooperation functionalities has been developed that enables the regio- and stereodivergent hydrogenation of allenes to provide all possible multisubstituted alkene products.
The production of fluorination agents generally involves the formation of toxic hydrogen fluoride. Now, a mechanochemical protocol to decompose the fluoropolymer polyvinylidene fluoride has been developed, generating potassium fluoride as a fluorinating agent. This approach provides a safer and sustainable fluorination strategy for efficient SâF, C(sp2)âF and C(sp3)âF bond formation.
Selective chemical upcycling of polyolefin mixtures remains challenging due to the structural similarity of their backbones. Now it has been shown that a single-site nickel catalyst can preferentially and efficiently cleave branched CâC bonds, enabling the hydrogenolytic separation of isotactic polypropylene from mixtures containing both isotactic polypropylene and polyethylene.
High-entropy nanomaterials, which incorporate multiple homogeneously dispersed elements, are promising for energy conversion, but typically require complex, high-temperature synthesis. Now a scalable flame synthesis method has been shown to produce tunable, high-entropy nanomaterials under facile conditions, enabling the design of advanced electrocatalysts for hydrogen peroxide production and other relevant applications.
The programmability of synthetic cells, comprising lipid vesicles that are capable of imitating the structure and function of living cells, facilitates their application as drug delivery devices. Now, magnetic hyperthermia has been used to control the on-demand synthesis and release of biomolecules from within synthetic cells.
Metalâsulfur motifs are commonly found in enzymatic active sites and heterogeneous catalysis, but they remain underexplored in porous solids. Now, sulfur-based ligands have been incorporated into metalâorganic frameworks through post-synthetic modifications. The resulting sulfide MOFs exhibit enhanced catalytic performance in the selective hydrogenation of nitroarenes compared with their parent MOFs containing terminal or bridging chloride and hydroxyl groups.
The synthesis of drug-like saturated cycloalkanes is more complex than their two-dimensional aromatic analogues. A formidable challenge lies in synthesizing all isomers of multi-substituted cycloalkanes. Now a cobalt-catalysed system enables diastereodivergent hydroalkylation of substituted methylenecyclohexanes with exceptional versatility. Strategic manipulation of ligands provides access to all isomers of disubstituted cyclohexanes, piperidines and multi-substituted cyclohexanes.
Subcellular lipid transport between organelles and turnover remain poorly explored due to the technical challenges associated with selective lipid labelling. Now a subcellular photocatalytic labelling strategy has been developed that allows organelle-specific lipid analysis and quantitative profiling of lipid transport.
Electrochemical energy-storage devices require rapid chargeâdischarge profiles, but the dense electrode packing required to achieve high energy densities results in sluggish ion-transport kinetics. Now a two-dimensional vertical ladder polymer cathode has been shown to achieve promising performance and tolerance by using a cross-flow lithium migration pathway.
Primary aliphatic amines are abundant building blocks but underutilized as alkyl sources in CâC bond formation. Now it has been shown that integrating nitrogen-atom deletion into the aza-Michael reaction redirects the classical pathway from (sp3)CâN bond formation to Giese-type (sp3)CâC(sp3) bond construction.
Amyloid fibrils can adopt a range of distinct conformations, yet it is challenging to rapidly discriminate between these polymorphs. Now methods have been developed to screen large, diverse libraries of turn-on fluorescent dyes to rapidly identify probes that recognize fibril subsets.
Azoles are important synthetic targets due to their diverse applications in areas ranging from human health to food security. Now it has been shown that the hydroazolation of alkenylthianthrenium salts provides a modular platform to access diverse, densely functionalized N-alkyl azole compounds with high N-regioselectivity.
Elucidating the nature of the metallocofactors in nitrogenase enzymes, and preparing synthetic analogues of these clusters, is a classic target for bioinorganic chemists. Now the transformation of [Fe2S2]2+ rhombs to [Fe8S8]n+ clusters has been achieved through a series of redox- and ligand-substitution reactions.
Current solid-phase peptide synthesis methods struggle to incorporate sterically hindered amino acids. Now researchers have developed a ribosome-mimicking molecular reactor that bypasses two-phase acyl transfer to boost the coupling efficiency of peptides containing N-methylated and/or α,α-disubstituted amino acids.
While the ligand coordination microenvironment surrounding catalytic centres influences reactivity, dynamic oxygen reconstruction during water oxidation electrocatalysis complicates structure-based mechanistic insights. Now the in situ formation of lattice OâO ligands has been shown to activate Fe centres in metal oxides and hydroxides, thereby enhancing their oxygen evolution reaction activity.